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Vinyl Diazonium Ions as Synthetic Intermediates

作为合成中间体的乙烯基重氮离子

基本信息

批准号：
2102229
负责人：
Matthias Brewer
金额：
$ 50万
依托单位：
University of Vermont & State Agricultural College
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2021
资助国家：
美国
起止时间：
2021-07-01 至 2024-06-30
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=2102229&HistoricalAwards=false
关键词：
Vinyl Diazonium Ions Synthetic Intermediates

项目摘要

With the support of the Chemical Synthesis Program in the Division of Chemistry, Professor Matthias Brewer of the University of Vermont is developing new ways to make organic molecules using compounds called vinyl diazonium ions to achieve new carbon-carbon bond connections. Vinyl diazonium ions are uncommon chemical building blocks with the potential to become important synthetic tools. Professor Brewer and his students are testing these compounds in complex synthetic examples and systematically establishing their fundamental reactivity. Investigating innovative strategies to prepare organic molecules is an important goal as it enables advances in many other fields of research that depend on complex organic molecule synthesis such as drug discovery and materials science. This program is being used to engage economically-disadvantaged high school students in science, technology, engineering, and mathematics (STEM) activities in collaboration with the American Chemical Society (ACS) Project SEED program. Professor Brewer is also organizing an annual retreat for University of Vermont students of color in STEM disciplines. This retreat will help to overcome the sense of isolation that students of color in STEM fields feel by providing these students a chance to meet and build a greater sense of community at the University of Vermont.Vinyl diazonium ions are underdeveloped synthetic intermediates with the potential to provide solutions to current synthetic challenges. Professor Brewer and his research team are investigating the reactivity of vinyl diazonium ions to provide new approaches to the synthesis of all-carbon quaternary centers, access complex structures that contain a diazo functional group, and provide a strategy towards the first total synthesis of anadensin, a fusicoccane diterpenoid with anti-cancer and anti-microbial activity. All-carbon quaternary centers in complex organic compounds are challenging to install due to their sterically encumbered nature but are found in many biologically active molecules including natural products that have been shown to be excellent medicinal leads. Vinyl diazonium ions are being studied as electrophiles to provide new stereoselective routes to all-carbon quaternary centers that are difficult to make by traditional methods. The diazo group is one of the most versatile functional groups in synthetic chemistry and the products formed by the addition of nucleophiles to vinyl diazonium ions are being explored as activated synthetic intermediates for subsequent complexity building reactions. Investigations towards the synthesis of anadensin are being used to test a new strategy for preparing complex dicyclopenta[a,d]cyclooctene 5-8-5 ring systems. These activities are synergistically providing important training in synthetic chemistry for a diverse group of graduate and undergraduate students at the University of Vermont.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

在化学系化学合成项目的支持下，佛蒙特大学的Matthias Brewer教授正在开发新的方法，使用称为乙烯基重氮离子的化合物来制造有机分子，以实现新的碳-碳键连接。乙烯基重氮离子是不常见的化学结构单元，具有成为重要合成工具的潜力。布鲁尔教授和他的学生正在复杂的合成实例中测试这些化合物，并系统地建立它们的基本反应性。研究制备有机分子的创新策略是一个重要的目标，因为它使许多其他依赖复杂有机分子合成的研究领域取得进展，如药物发现和材料科学。该计划被用于与美国化学学会（ACS）项目SEED计划合作，让经济上处于不利地位的高中生参与科学，技术，工程和数学（STEM）活动。布鲁尔教授还为佛蒙特大学STEM学科的有色人种学生组织年度务虚会。这次务虚会将有助于克服STEM领域的有色人种学生所感受到的孤立感，为这些学生提供一个在佛蒙特大学见面并建立更大社区感的机会。乙烯基重氮离子是欠发达的合成中间体，有可能为当前的合成挑战提供解决方案。Brewer教授和他的研究团队正在研究乙烯基重氮离子的反应性，以提供合成全碳季中心的新方法，获得含有重氮官能团的复杂结构，并为首次全合成anadensin提供策略，anadensin是一种具有抗癌和抗微生物活性的fusicoccane二萜类化合物。复杂有机化合物中的全碳季中心由于其空间阻碍的性质而具有挑战性，但在许多生物活性分子中发现，包括已被证明是优秀的药用先导物的天然产物。乙烯基重氮离子作为亲电试剂正在研究中，它为传统方法难以制备的全碳季铵中心提供了新的立体选择性路线。重氮基团是合成化学中最通用的官能团之一，并且通过亲核试剂加成到乙烯基重氮离子上形成的产物正在被探索作为后续复杂构建反应的活化合成中间体。对anadensin合成的研究被用于测试制备复杂二环戊[a，d]环辛烯5-8-5环系统的新策略。这些活动协同为佛蒙特大学的研究生和本科生提供了重要的合成化学培训。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。